Through comparing the photocatalytic performance of rnicroscale ZnO, nano ZnO, and Degussa P25 titania (P25), it was found that the microscale ZnO exhibited 2.6-35.7 times higher photocatalytic activity for the photodegradation of various dye pollutants than P25 Under both UV-visible and visible it-radiation and showed much better photostability than the nano ZnO. The photocatalysts were characterized with XRD, Raman, BET, DRUV-vis, adsorption of dye, photoelectrochemical measurement, and PL. The Much higher photocataltyic activity of the rnicroscale ZnO than P25 under UV-visible irradiation is attributed to the higher efficiency of generation,mobility,and separation of photoinduced electrons and holes. The much higher visible photocataltyic activity of the microscale ZnO than P25 is due to the higher photosensitization efficiency of electron transfer from all excited dye to the conduction band of the rnicroscale ZnO than that of P25. The much better photostability of the microscale ZnO than the nano ZnO is due to its better crystallinity and lower defects. The photostability of the microscale ZnO is greatly improved by the surface modification of ZnO with a small amount of TiO2. On the basis of the excellent photocatalytic performance of the rnicroscale ZnO and TiO2-modified ZnO, a novel device of coupling photodegradation with light-to-electricity conversion was developed, which is a promising candidate for the photocatalytic removal of dye pollutants and a renewable energy source.